Coloring hydrophobic fibers using carrier of halogenated hydroxybiphenylether

ABSTRACT

Organic hydrophobic fibers are colored using a disperse or cationic dyestuff employing a carrier component of a halogenated hydroxybiphenylether.

United States Patent [191 Dellian et a1.

Inventors: Kurt A. Dellian, Spring Valley;

Thomas A. Furia, Hartsdale, both of NY.

Assignee: Ciba-Geigy Corporation, Ardsley,

Filed: Mar. 6, 1972 Appl. No.: 232,191

US. Cl. 8/173, 260/613 R Int. Cl D06p 5/04 Field of Search 8/173; 260/613 R June 11, 1974 [56] References Cited UNITED STATES PATENTS 2,270,706 1/1942 Heymann 8/173 3,385,652 5/1968 Walter et a1. 8/173 X 3,506,720 4/1970 Model et a1 260/613 R Primary Examiner-J'homas .1. Herbert, Jr. Attorney, Agent, or Firm-Mr. Joseph G. Kolodny; Mr. Stanley A. Marcus; Dr. E. McC Roberts 57] ABSTRACT Organic hydrophobic fibers are colored using a disperse or cationic dyestuff employing a carrier component of a halogenated hydroxybiphenylether.

.6 Claims, No Drawings COLORING HYDROPIIOBIC FIBERS USING CARRIER OF IIALOGENATED l-IYDROXYBIPHENYLETH ER BACKGROUND OF THE INVENTION The present invention isdirectedito aprocess forcoloring as through dyeing or: printing hydrophobic organic polymer fibers employing anladditional. carrier component. 7

It is well'known in the prior art techniques of dyeing and printing that special procedures are necessary to color a textile structure of fabric that is essentially water impermeable. since otherwise serious problems arise. For example, with, many conventional techniques, the dyestuffi'doesnot penetrate the. water impermeable material and does not affect coloration. In the event coloration does occur, it is not: permanent and leaches out during subsequent washing steps.

To circumvent the problems ofthenoncoloration or the leaching of the-dye, theprior art: has employed in the treatment of the hydrophobic,syntheticfibers elevated pressures with temperatures greater generally than 250 F. Generally speaking, dyeingunder'pressure at'elevated temperature is undesirable duezto expensive and complex procedures. To bypass this dyeing technique, the prior art has also turned-to specific carrier components. These carriers aid in the penetration. of the dye into the fiber by causinga swelling of the base substrate.

The use of carriers in dyeing techniquesupon hydrophobic fibers allows satisfactory resultsattemperatures as low as 200 to 210 F although a temperature of 212 F at normal atmospheric pressure ispreferred. There are many carrier components for hydrophobic fibers known in the prior art to be employed' with avariety ofdyes. Among the typical carriers used by the art up to the present time are various derivatives of benzene and. phenol such as orthoand para-phenylphenol, chlorinated benzenes, xylenes, naphthalenes. toluenes, aromatic esters or ethers, and biphenyl. Nevertheless. many of these carrier components have some drawbacks such as lack of availability, undue toxicity, lack of ease of removal from the substrate, effect on lightfastness of color, or influence of buildup of a heavyshade.

It is an object of this inventionto provide. a novel'carrier component which is suitable for dyeing hydrophobic material.

DESCRIPTION OF THE INVENTION halogenated hydroxybiphenylether. This carrier is of the following formula:

wherein I X is halogen,

n is an integer from 0 to 3, Y is chlorine or bromine, m is an-integer from 0 to 3, the sum of n andm is, l, to 3;

Apreferred class ofcompounds within the above definition is when X and Y, are specific to chlorine.

The carriers of this invention of the halogenated hydroxybiphenylether type are found in US. Pat. No. 3,506,720 issuedjApr. I4, 1970. The disclosure of this patent is incorporatedrby reference herein.

Thecarrier compounds of the present invention are, in most cases, clear colorlesssolids. They are utilized in the form of. an emulsion or dispersion composition which is added to the, dyebath formulation, printing paste, or prescouringbath. Besides the carrier activity they possess a bacteriostatic, action.

The carriers of the present invention are generally colorless, odorless and non-toxic, or nearlyso. They usually do notgaffectthe fastness other than by improving it, and are either non-foaming or very low foaming. Dyeing processes utilizing, the carrier composition of the present invention exhibit a slow drawing of the dyestuff resulting in excellent levelness and extremely good. utilization or exhaustion of the dyestuff.

The types of dyestuffs employable in the present invention are well known in the art as disperse and cationicdyestuffs. Illustrative although not limiting of suitable disperse dyestuffs are those listed in the Color Index under the Disperse dye classification.

There, are various techniques and procedures for dyeing the synthetic fibrous material utilizing'the disperse or'cationic dyestuff and carrier component disclosed herein. As employed. herein, a fabrous material includes fibers,,yarns, threads, fabric ribbons, tapes and tabs.

Thedyestuff andemulsified carrier may be added to a bath at temperatureequivalent to the boiling point of water. A time interval of two or three hours is utilized during; which time the fibrous substrate is contacted with the dyebath composition. Thereafter the fabric is washed followed by drying.

Another technique of applying the dyestuff in emulsified carrier with with a composition containing the dyestuff carrier and emulsifying agent which is applied by padder on the substrate followed by steaming for a time period of 10 of 15 minutes.

Insofar as printing techniques are concerned printing may be carried out in the usual way by adding the carrier emulsionto a paste and'printing the material on a roller or screen printing unit followed by fixing the dye by exposing to steamor. heat treatment.

A thermosol technique may be utilized by padding the material, with a mixture of a, disperse dye-emulsified carrier of the type disclosed herein followed by drying at to 250 C for l to 30 minutes. Alternatively thennofixing may take place with steam injection at temperature-time conditions as 340 F for l to 30 minutes.

The types of substrates that may be employed as previously disclosed are hydrophobic materials that do not color readily without theuse of a carrier component. Suitable examples of the hydrophobic material include 3 polyester and acid'modified polyester, polyamide, cationic dyeable polyamide, polypropylene, polyacrylonitrile, and its modified versions, modacrylics, or triacetate.

As indicated above, the carriers of this invention are generally employed in the form of an emulsion in order to achieve rapid and uniform distribution of the carriers in the prescouring bath, dyebath, or printing composition. The emulsifying agents which are employed may generally be of the cationic, anionic, or nonionic type of surface active agents familiar to those skilled in the art. Representative of those surface active agents are those of the following formulae in which R is alkyl and M is a metallic cation such as sodium or potassium, or ammonium and derivatives thereof:

1. R-COOM wherein R is an alkyl group containing 7 to 24 carbon atoms. 2. ROSO OM wherein R is an alkyl group containing 7 to 24 carbon atoms.

3. R50 M wherein R is an alkyl group containing 12 to 18 carbon atoms.

4. R-Ar-SO M wherein R is an alkyl group containing 3 to 18 carbon atoms and Ar is an aromatic nucleus selected from benzene, naphthalene, anthracene, etc.

5. R-Ar-(OCH CH2) --OSO3 M 01' wherein R is an alkyl substituent on a benzene ring containing 1 to 18 carbon atoms and Ar is a benzene nucleus and z is at least one and as high as l0.

6. R--A'r--(OCH CH ),--OH wherein R is an alkyl group containing l t o l8 carbon atoms. Ar is a benzene nucleus and z is a number from 4 to 40.

7. R--(OCH CH OH wherein R is an alkyl group containing 7 to 24 carbon atoms and z is a number from 4 to 40.

8. R--(OCH CH --OSO M wherein R is an alkyl group containing 8 to 24 carbon atoms and z is a number equaling l to 4.

9. R--C--O--(OCH CH OH wherein R is a fatty radical containing 8 to 24 carbon atoms and z is anumber equaling 4 to 40.

wherein R is an alkyl or amido group containing 8 to 24 carbon atoms, R, is hydrogen, alkyl or an aralkyl group R is hydrogen or an alkyl group containing 1 to 8 carbon atoms, R, is hydrogen, alkyl or aralkyl group and X is an anionic radical, e.g. chloride, sulfate or sulfate derivative.

Representative of specific emulsifying agents which may be employed are lauryl dimethyl, benzylammonium chloride, Turkey red oil, sodium lauryl sulfate, sodium dodecyl benzene sulfonate, triethanolamine salt of lauryl sulfate, ethoxylated nonylphenol and the like.

Especially preferred is the sodium lester sulfate.

Where cationic dyes are used the emulsifier desirably are of the nonionic or cationic type. Nonionic agents are preferred in most instances.

The dye carrier composition is prepared by blending together from about 10 to about 90 parts (by weight) of carrier and from about 10 to about 90 parts (by weight) of the emulsifying agent. The emulsion ordinarily is prepared in water in a known manner. A preferred embodiment employs for 50 parts to 80 parts carrier in conjunction with 20 to 50 parts of emulsifying agent. Especially preferred is a composition of about 70 carrier and about 30 parts emulsifier.

Experience has indicated that dye carriers of the present invention, besides being generally free of undesirable color, odor, foaming irritant, and toxic properties, are two to three times more effective on a weight to weight bases than previously employed carriers such as biphenyl, methyl naphthalene, o-phenyl and others.

salt of oleylamy To further illustrate the innovative aspects of the present invention the following examples are provided:

EXAMPLE 1 A dye carrier composition is prepared by melting 80 parts by weight of 2-hydroxy 2, 4, 4, trichlorodiphenylether, l0 parts of the sodium salt of nonylphenoxypolyethylenoxyl ethanol and 10 parts of the sodium salt of oleyl amylester sulfate. After cooling the mixture is pulverized. The dyebath is loaded at 50 C with Dacron (polyethylene terepthalate) double knit at a liquor ratio of 40:]. Based on the weight of fabric (owf), 2% of the following dyestuff is employed:

5.. i i O a)2 N \C EXAMPLE 2 The procedure of Example 1 is repeated but employing 3 parts by weight of the fiber of a dyestuff of the formula:

Boron; 2

OzN

A strong reddish brown shade. of excellent light fastness is obtained.

EXAMPLE 3 A printing paste is prepared containing parts of the carrier composition described in Example 1, 2.5

parts of a dyestuff of the formula:

3 parts sodium alginate thickener, and 20 parts mineral spirits. A polyethylene terephthalate cloth is printed with the paste and then the printed cloth is cured for l minute at 3509() F. The cloth is then soaped and rinsed. A vivid reddish blue shade is obtained.

EXAMPLE 4 Following the general procedure of Example 1, a fabric of acid modified polyethylene terephthalate (Dacron 64) is dyed using 1.5 parts of a dyestuff of the formula:

However, this procedure employs ethoxylated nonylphenol in place of the sodium salt of oleyl amylester sulfate. A brilliant pink shade having good fastness properties is obtained.

EXAMPLE 5 The procedure of Example 1 is repeated but employing 2.5 parts of the dystuff of the formula:

and 6 parts of the carrier emulsion composition. A vivid pink shade of excellent fastness is obtained.

EXAMPLE 6 A dye carrier composition is prepared in like manner as Example 1, but instead of 2 hydroxy 2'4, 4 trichlorodiphenylether, 2 hydroxy 4,4 dichlorodiphenylether is used. In this example, the following dyestuff is added:

@el g A liquor ratio of 40:1 is present in the dye bath with 100 pounds of polyethylene terephthalate (Dacron 54) fabric. Initially the bath temperature is at 140 F followed by raising the temperature to boiling over a period of 20 minutes which is maintained for minutes. The fabric is rinsed, soaped, and placed in a bath of 2% hydrosulfite and 2% weight soda ash for 15 minutes at 180 F. A brilliant yellow shade having excellent fastness properties results.

EXAMPLE 7 With the dyebath keep at boiling, the dyeing procedes for a periodof 60 minutes. The fabric is rinsed and treated with hydrosulfated soda ash, soaped and again rinsed. A deep brown shade having excellent fastness properties is obtained.

EXAMPLE 8 The procedure of Example 6 is repeated but employing the dyestuff of the formula:

2 (Ben.

A very deep orange shade results.

EXAMPLE 9 The procedure of Example 1 is repeated but employing instead of 2 hydroxy 2,4, 4' trichlorobiphenylether, 2 hydroxy 4 chloro biphenyl ether. Additionally, the following dyestuff is substituted.

A blue shade of good fastness results.

, EXAMPLE The procedure of Example 1 is repeated but using a mixture of the following dyestuff are employed at equal concentrations:

A brilliant violet shade of excellent fastness results.

EXAMPLE 11 The procedure of Example I is repeated in all essential respects but instead of Dacron, a fabric of Nylon 66 (polyamidc) is used.

A strong shade of yellow is obtained.

What is claimed is:

1. In a process for coloring fibrous material selected from the group consisting of polyester, polyamide, polypropylene, polyacrylonitrile and triacetate with a disperse or cationic dyestufi' with the aid of a carrier component in an emulsion or dispersion, the improvement comprising utilizing a carrier component of the following formula:

rial is a polyamidel said halogen is 

2. The process of claim 1 wherein said halogen is chlorine or bromine.
 3. The process of claim 2 wherein said halogen is chlorine.
 4. The process of claim 1 wherein both X and Y represent chlorine.
 5. The process of claim 1 wherein said fibrous material is a polyester.
 6. The process of claim 1 wherein said fibrous material is a polyamide. 